CN110534759A - A kind of fuel cell Fe-N-C non-precious metal catalyst and preparation method thereof - Google Patents
A kind of fuel cell Fe-N-C non-precious metal catalyst and preparation method thereof Download PDFInfo
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- CN110534759A CN110534759A CN201910684308.5A CN201910684308A CN110534759A CN 110534759 A CN110534759 A CN 110534759A CN 201910684308 A CN201910684308 A CN 201910684308A CN 110534759 A CN110534759 A CN 110534759A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a kind of fuel cell Fe-N-C non-precious metal catalysts, wherein carrier is the graphite mould carbon formed after melamine and iron complex compound high temperature cabonization, active component is in the equally distributed iron of graphite mould carbon surface and its carbide, preparation method is with anhydrous ferric chloride and pyridine -2,6- dicarboxylic acids reacts under thermal and hydric environment, the novel crystalline material iron complex compound with acicular texture of one kind formed by self assembly coordination, then melamine and iron complex compound are uniformly dispersed, are then calcined under high temperature；Non-precious metal catalyst dispersion provided by the present invention is relatively uniform, used cost of material is all relatively cheap, cost is significantly reduced, and shows excellent electro catalytic activity and stability under alkaline condition, meets the requirement of fuel cell non-precious metal catalyst at this stage.
Description
Technical field
The invention belongs to fuel cell non-precious metal catalyst technical fields, and in particular to a kind of novel Fe-N-C is non-
Noble metal catalyst and preparation method thereof.
Background technique
With being on the rise for environmental pollution and energy shortage problem, the exploitation of new energy and new energy device just seems pole
To be urgent, Hydrogen Energy is one kind of numerous new energy, and it is high, pollution-free to have many advantages, such as specific energy, and fuel cell is as a kind of
The enthusiasm of extensive research both at home and abroad directly can be caused using the clean energy resource device of Hydrogen Energy, it can be by fuel (usually
Hydrogen) and oxidant in chemical energy be converted into electric energy, and have many advantages, such as that pollution-free, efficient energy conversion is high.
The core component of fuel cell is membrane electrode, it is electrochemical reaction of fuel battery, is multinomial mass transfer place,
Wherein catalyst is the critical material of fuel cell membrane electrode assembly, and the superiority and inferiority of catalyst performance determines the output of fuel cell
Efficiency, and catalyst used in fuel cell is mainly platinum based catalyst at present, but the high cost of platinum based catalyst and have
The reserves of limit limit the large-scale application of fuel cell, in order to realize the sustainable development of fuel cell, carry out base metal
The research of catalyst has very great meaning.But non-precious metal catalyst compared with platinum based catalyst rise catalytic activity and
The uniform larger gap of stability, and the catalytic mechanism of non-precious metal catalyst is still not clear, it is therefore desirable to base metal is urged
Agent is deeply probed into, and identifies its active site and catalytic mechanism, and preparation takes into account the base metal of activity and stability
Catalyst.
The type of non-precious metal catalyst is many at present, is broadly divided into following three kinds:
1) transition metal-nitrogen-C catalyst, such catalyst are mainly made of three kinds of transition metal, nitrogen and carbon elements, and kind
A kind of non-precious metal catalyst that class is most abundant, most study, activity are best；
2) transistion metal compound, mainly including some transition metal oxides, chalcogen compound, carbide and nitride, but
It is that these compounds usually require to do some surface treatments；
3) non-metallic catalyst, the usually carbon material of Heteroatom doping, without easily by acid corrosion in non-metallic catalyst
Base metal thus often has preferable stability under acidic environment.
Summary of the invention
It is prepared simply the object of the present invention is to provide a kind of, cost is relatively low, and has high catalytic activity and stability good
Fuel cell non-precious metal catalyst and preparation method thereof.To realize the purpose, this invention takes following technical schemes:
A kind of fuel cell Fe-N-C non-precious metal catalyst, structure are that carbon carries Fe and Fe3C, and wherein carrier is melamine
The graphite mould carbon formed after amine and iron complex compound high temperature cabonization, active component are in the equally distributed iron of graphite mould carbon surface
And its carbide.
A kind of fuel cell preparation method of Fe-N-C non-precious metal catalyst, steps are as follows:
(1) it weighs a certain proportion of anhydrous ferric chloride and pyridine -2,6- dicarboxylic acids is dissolved in deionized water, ethyl alcohol and N, N- dimethyl
In the mixed solution of formamide, 12h~36h is reacted under 180 DEG C~240 DEG C hydrothermal conditions, it is cooling to filter drying, obtain red
Iron complex compound；
(2) a certain proportion of iron complex compound and melamine are weighed in ethylene glycol solvent, ultrasonic agitation is uniformly dispersed, and stirs
Mixing the time is 6~12h, and filtration drying obtains non-precious metal catalyst presoma；
(3) non-precious metal catalyst presoma is placed in porcelain boat, carries out high temperature using tube type high-temperature furnace under nitrogen atmosphere and forges
2~12h of processing is burnt, fuel cell Fe-N-C non-precious metal catalyst is obtained.
Further, the ratio of anhydrous ferric chloride and pyridine -2,6- dicarboxylic acids is 1:1~5:1 in the step (1).
Further, the ratio of deionized water, ethyl alcohol and n,N-Dimethylformamide is 1~3:1~3 in the step (1):
1~3.
Further, iron complex compound and melamine mass ratio are 20mg~100mg:1g in the step (2).
Further, drying temperature is 50 DEG C~70 DEG C in the step (1) and (2), and drying time is 12h~for 24 hours.
Further, calcination temperature is 600 DEG C~950 DEG C in the step (3), and calcination time is 3h~6h.
The beneficial effects of the present invention are:
The present invention, which is reacted under thermal and hydric environment with anhydrous ferric chloride with organic ligand pyridine -2,6- dicarboxylic acids, generates a kind of novelty
The metal organic complex material with acicular texture, by being prepared for a kind of novel fuel with melamine mixed calcining
Battery non-precious metal catalyst, hence it is evident that reduce preparation cost, the further development of non-precious metal catalyst will be promoted.
By carrying out structural characterization to prepared product, it was demonstrated that after being carbonized in fact with iron complex compound and melamine
Graphite mould carbon is carrier, and iron and carbide particle are dispersed in graphite mould carbon surface, observes discovery metallic particles by Electronic Speculum
Distribution uniform has excellent electro catalytic activity and stability under alkaline condition.
Detailed description of the invention
Fig. 1 is preparation method flow chart of the invention；
Fig. 2 is XRD diagram of the invention；
Fig. 3 is iron complex compound transmission electron microscope picture；
Fig. 4 is transmission electron microscope picture of the invention；
Fig. 5 is high-resolution-ration transmission electric-lens figure of the invention；
Fig. 6 is the catalyst of different content iron complex compound preparation and the polarization curve comparison diagram of platinum carbon catalyst.
Specific embodiment
Catalyst prepared by the present invention belongs to transition metal-nitrogen-C catalyst, and the presoma of selection is that a kind of Novel iron is matched
Position compound and melamine, iron complex compound are one kind of MOFs material, and MOFs material is by transition metal and organic to match
Body has the porous material of three-dimensional framework material by one kind that self assembly is interconnected to form, and this kind of material has specific surface
The advantages that product is big, stable structure, and usually there is three kinds of transition metal, nitrogen and carbon elements simultaneously, it is ideal base metal
The presoma of catalyst.
Non-precious metal catalyst of the invention prepares a kind of novel iron complex compound with acicular texture, so first
Iron complex compound is mixed with melamine afterwards and is uniformly dispersed, finally pyrolysis is prepared, and structure is carbon-supported metal activity
Site, wherein carrier is the graphite mould carbon formed after melamine and iron complex compound high temperature cabonization, and active component is in stone
The equally distributed iron of black type carbon surface and its carbide.The present invention is done furtherly below by the drawings and specific embodiments
It is bright, but it is not meant to limiting the scope of the invention.
Fuel cell non-precious metal catalyst of the invention includes carrier and active component, and carrier is melamine and iron
The graphite mould carbon formed after complex high temperature cabonization, active component are in the equally distributed iron of graphite mould carbon surface and its carbon
Compound.
As shown in Figure 1, preparation method of the invention includes two big steps, it is anti-by controlling first with hydro-thermal reaction method
PH, reaction temperature and the time answered synthesize iron complex compound, are then uniformly mixed melamine and iron complex compound,
The presoma that upper step is obtained is in N2Lower high-temperature calcination prepares iron complex compound doping melamine catalyst.Specific steps are such as
Under:
The preparation of iron complex compound:
(1) it weighs anhydrous ferric chloride and pyridine -2,6- dicarboxylic acids is dissolved in deionized water, ethyl alcohol and N,N-dimethylformamide mixing
In solution, 12~36h is reacted under 180 DEG C~240 DEG C hydrothermal conditions, it is cooling to filter drying, obtain red iron complex compound.
(2) iron complex compound obtained by the step of weighing certain proportion (1) and melamine are in ethylene glycol solvent, ultrasound
It is dispersed with stirring uniformly, mixing time is 6~12h, and filtration drying obtains non-precious metal catalyst presoma；
(3) non-precious metal catalyst presoma obtained by step (2) is placed in porcelain boat, in N2Using tube type high-temperature furnace to it under atmosphere
It carries out high-temperature calcination and handles 6~6h, obtain fuel cell Fe-N-C catalyst.
Embodiment 1
(1) 20mg iron complex compound and 1g melamine are weighed in 100ml beaker, 10~20ml ethylene glycol, ultrasound is added
Stirring makes it be uniformly dispersed, and 6~12h is stirred at room temperature, and filters drying；
(2) by composite material obtained by (1) in porcelain boat, in N2Under atmosphere, using tube furnace to it high temperature at 600~950 DEG C
3~6h is handled to get non-precious metal catalyst.
Embodiment 2
(1) 40mg iron complex compound and 1g melamine are weighed in 100ml beaker, 10~20ml ethylene glycol, ultrasound is added
Stirring makes it be uniformly dispersed, and 6~12h is stirred at room temperature, and filters drying；
(2) by composite material obtained by (1) in porcelain boat, in N2Under atmosphere, using tube furnace to it high temperature at 600~950 DEG C
3~6h is handled, to get non-precious metal catalyst.
Embodiment 3
(1) 60mg iron complex compound and 1g melamine are weighed in 100ml beaker, 10~20ml ethylene glycol, ultrasound is added
Stirring makes it be uniformly dispersed, and 6~12h is stirred at room temperature, and filters drying；
(2) by composite material obtained by (1) in porcelain boat, in N2Under atmosphere, using tube furnace to it high temperature at 600~950 DEG C
3~6h is handled to get non-precious metal catalyst.
Embodiment 4
(1) 80mg iron complex compound and 1g melamine are weighed in 100ml beaker, 10~20ml ethylene glycol, ultrasound is added
Stirring makes it be uniformly dispersed, and 6~12h is stirred at room temperature, and filters drying；
(2) by composite material obtained by (1) in porcelain boat, in N2Under atmosphere, using tube furnace to it high temperature at 600~950 DEG C
3~6h is handled to get non-precious metal catalyst.
Embodiment 5
(1) 100mg iron complex compound and 1g melamine are weighed in 100ml beaker, 10~20ml ethylene glycol, ultrasound is added
Stirring makes it be uniformly dispersed, and 6~12h is stirred at room temperature, and filters drying；
(2) by composite material obtained by (1) in porcelain boat, in N2Under atmosphere, using tube furnace to it high temperature at 600~950 DEG C
3~6h is handled to get non-precious metal catalyst.
Structural characterization is carried out to the product of embodiment 1-5 preparation, it was demonstrated that its carrier is melamine and iron complex compound
The graphite mould carbon formed after high temperature cabonization, active component are in the equally distributed iron of graphite mould carbon surface and its carbide, averagely
Partial size is 14.33nm, Electronic Speculum observation discovery catalyst granules distribution uniform.
X ray diffraction analysis x
X-ray diffraction is carried out to catalyst prepared by the present invention, analyzes its diffracting spectrum.As shown in Fig. 2, in XRD diagram, in 2 θ
=26.2 ° of diffraction maximum belongs to graphitic carbon (002), and graphitic carbon is by the organic ligand and melamine in iron complex compound
It is formed by pyrolysis.44.6 ° and 65 ° of diffraction maximum corresponds respectively to (110) and (200) crystal face of α-Fe, remaining spreads out
Penetrate peak and Fe3C(JCPDS NO.89-2867) it is corresponding, after showing high-temperature process, the iron ion of iron complex compound is reduced
For Fe and Fe3C.Iron complex compound doping melamine eventually passes through the Fe/ that high-temperature heat treatment successful conversion is N doping
Fe3C-C。
Transmission electron microscope analysis
Transmission electron microscope analysis is carried out to catalyst prepared by the present invention.It is analyzed by the transmission electron microscope picture to iron complex compound
It was found that iron is coordinated after Fig. 4 can be seen that calcining as shown in figure 3, iron complex compound is in irregular acicular crystal shape
Compound crystal structure is destroyed, and the nitrogenous organic ligand carbonization in crystal is combined into organic carbon with melamine carbonization
Layer, the iron ion according to the XRD in crystal are converted after high-temperature calcination for iron simple substance and its carbide, these metals from
Son is dispersed in organic carbon layer surface.By the high resolution electron microscopy photo for adulterating melamine catalyst to iron complex compound
(Fig. 5) analysis finds that metallic particles is coated by graphite carbon-coating, and the lattice fringe through measurement discovery metallic particles is 0.21nm,
Corresponding to Fe3(211) crystal face of C, it is consistent with XRD result.
Electro catalytic activity analysis
Electricity is being carried out to catalyst prepared by the present invention under alkaline condition using electrochemical workstation and rotating disk electrode (r.d.e) device
Catalytic performance analysis, result are as shown in Figure 6, it can be seen that a series of catalytic activity of prepared catalyst all has excellent
Electro catalytic activity, in addition to iron complex compound content be 100mg catalyst other than, the catalytic activity of other catalyst is above
The activity of business platinum carbon catalyst, the catalyst that wherein iron complex compound content is 40mg have best catalytic activity,
Its take-off potential has reached 1.05V.
The present invention is prepared for iron complex compound using hydro-thermal reaction method, passes through high-temperature calcination iron complex compound and trimerization
Cyanamide is prepared for iron complex compound doping melamine catalyst.Non-precious metal catalyst prepared by the present invention has price just
Preferably, (specific surface area of catalyst is about 110.301m to specific surface area height2/ g), the advantages that catalytic activity height and high chemical stability,
Fuel cell will be promoted further to develop.
The above-described embodiments merely illustrate the principles and effects of the present invention, and the embodiment that part uses, for
For those skilled in the art, without departing from the concept of the premise of the invention, can also make it is several deformation and
It improves, these are all within the scope of protection of the present invention.
Claims (7)
1. a kind of fuel cell Fe-N-C non-precious metal catalyst, it is characterised in that: carrier is melamine and iron coordinationization
The graphite mould carbon formed after object high temperature cabonization is closed, active component is in the equally distributed iron of graphite mould carbon surface and its carbide.
2. a kind of preparation method of Fe-N-C non-precious metal catalyst as described in claim 1, which is characterized in that steps are as follows:
(1) it weighs a certain proportion of anhydrous ferric chloride and pyridine -2,6- dicarboxylic acids is dissolved in deionized water, ethyl alcohol and N, N- dimethyl
In the mixed solution of formamide, 12h~36h is reacted under 180 DEG C~240 DEG C hydrothermal conditions, it is cooling to filter drying, obtain red
Iron complex compound；
(2) a certain proportion of iron complex compound and melamine are weighed in ethylene glycol solvent, ultrasonic agitation is uniformly dispersed, and stirs
Mixing the time is 6h~12h, and filtration drying obtains non-precious metal catalyst presoma；
(3) non-precious metal catalyst presoma is placed in porcelain boat, carries out high temperature using tube type high-temperature furnace under nitrogen atmosphere and forges
Burning processing, obtains fuel cell Fe-N-C non-precious metal catalyst.
3. a kind of preparation method of the fuel cell according to claim 2 with Fe-N-C non-precious metal catalyst, feature
It is, the ratio of anhydrous ferric chloride and pyridine -2,6- dicarboxylic acids is 1:1~5:1 in the step (1).
4. a kind of preparation method of the fuel cell according to claim 2 with Fe-N-C non-precious metal catalyst, feature
It is, the ratio of deionized water, ethyl alcohol and n,N-Dimethylformamide is 1~3:1~3:1~3 in the step (1).
5. a kind of preparation method of the fuel cell according to claim 2 with Fe-N-C non-precious metal catalyst, feature
It is, iron complex compound and melamine mass ratio are 20mg~100mg:1g in the step (2).
6. a kind of preparation method of the fuel cell according to claim 2 with Fe-N-C non-precious metal catalyst, feature
It is, drying temperature is 50 DEG C~70 DEG C in the step (1) and (2), and drying time is 12h~for 24 hours.
7. a kind of preparation method of the fuel cell according to claim 2 with Fe-N-C non-precious metal catalyst, feature
It is, calcination temperature is 600 DEG C~950 DEG C in the step (3), and calcination time is 3h~6h.
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| CN112014336A (en) * | 2020-08-18 | 2020-12-01 | 济南大学 | Universal method for detecting activity of alpha-glucosidase based on cascade reaction |
| CN113540476A (en) * | 2021-09-14 | 2021-10-22 | 南京大学 | Preparation method and application of non-noble metal cathode catalyst of fuel cell |
| CN115505957A (en) * | 2022-09-27 | 2022-12-23 | 四川轻化工大学 | Nickel-nitrogen doped carbon material for synthesizing hydrogen peroxide by electrocatalysis and preparation method thereof |
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Application publication date: 20191203 |